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dc.rights.licenseopenen_US
hal.structure.identifierChimie et Biologie des Membranes et des Nanoobjets [CBMN]
dc.contributor.authorDELAMARE, Aline
hal.structure.identifierChimie et Biologie des Membranes et des Nanoobjets [CBMN]
dc.contributor.authorNAULET, Guillaume
dc.contributor.authorKAUFFMANN, Brice
hal.structure.identifierChimie et Biologie des Membranes et des Nanoobjets [CBMN]
dc.contributor.authorGUICHARD, Gilles
IDREF: 084339268
hal.structure.identifierChimie et Biologie des Membranes et des Nanoobjets [CBMN]
dc.contributor.authorCOMPAIN, Guillaume
dc.date.accessioned2023-04-26T13:08:12Z
dc.date.available2023-04-26T13:08:12Z
dc.date.issued2022-07-20
dc.identifier.issn2041-6539en_US
dc.identifier.urihttps://oskar-bordeaux.fr/handle/20.500.12278/173216
dc.description.abstractEnThe isobutyl side chain is a highly prevalent hydrophobic group in drugs, and it notably constitutes the side chain of leucine. Its replacement by a hexafluorinated version containing two CF3 groups may endow the target compound with new and advantageous properties, yet this modification remains overlooked due to the absence of a general and practical synthetic methodology. Herein, we report the first general method to introduce the hexafluoroisobutyl group into ketoesters, malonates, 1,3-diketones, Schiff base esters and malononitrile. We demonstrated that the reaction occurs through an elimination/allylic shift/hydrofluorination cascade process which efficiently overcomes the usual fluoride β-elimination observed with α-CF3-vinyl groups. We showed that with alkali metal bases, a pentafluorinated alkene is obtained predominantly, whereas the use of tetrabutylammonium fluoride (TBAF) allows hydrofluorination to occur. This tandem process represents a conceptually new pathway to synthesize bis-trifluoromethylated compounds. This methodology was applied to the multigram-scale synthesis of enantiopure (S)-5,5,5,5′,5′,5′-hexafluoroleucine.
dc.description.sponsorshipInteractions supramoléculaires sélectives et directionnelles à base de synthons fluorés hautement polaires - ANR-20-CE06-0008en_US
dc.language.isoENen_US
dc.rightsAttribution-NonCommercial 3.0 United States*
dc.rights.urihttp://creativecommons.org/licenses/by-nc/3.0/us/*
dc.title.enHexafluoroisobutylation of enolates through a tandem elimination/allylic shift/hydrofluorination reaction
dc.title.alternativeChem. Sci.en_US
dc.typeArticle de revueen_US
dc.identifier.doi10.1039/D2SC02871Aen_US
dc.subject.halChimie/Matériauxen_US
bordeaux.journalChemical Scienceen_US
bordeaux.page9507-9514en_US
bordeaux.volume13en_US
bordeaux.hal.laboratoriesCBMN : Chimie & de Biologie des Membranes & des Nano-objets - UMR 5248en_US
bordeaux.issue33en_US
bordeaux.institutionUniversité de Bordeauxen_US
bordeaux.institutionBordeaux INPen_US
bordeaux.institutionCNRSen_US
bordeaux.peerReviewedouien_US
bordeaux.inpressnonen_US
hal.identifierhal-04082573
hal.version1
hal.date.transferred2023-04-26T13:08:15Z
hal.exporttrue
dc.rights.ccCC BYen_US
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Chemical%20Science&rft.date=2022-07-20&rft.volume=13&rft.issue=33&rft.spage=9507-9514&rft.epage=9507-9514&rft.eissn=2041-6539&rft.issn=2041-6539&rft.au=DELAMARE,%20Aline&NAULET,%20Guillaume&KAUFFMANN,%20Brice&GUICHARD,%20Gilles&COMPAIN,%20Guillaume&rft.genre=article


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